Fluoro-alkyl-substituted polynitroamines

ABSTRACT

1. THE COMPOUNDS HAVING THE FORMULA:   1-((2,4,6-TRI(X-),3-R-PHENYL)-NH-),2,4,6-TRI(Y-),R1-BENZENE   WHERE R AND R1 EACH REPRESENTS A FLUORO-ALKYL RADICAL HAVING FROM 1 TO 5 CARBON ATOMS, X REPRESENTS A NITRO RADICAL AND Y IS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND A NITRO RADICAL.

United States Patent 3,562,332 FLUORO-ALKYL-SUBSTITUTED POLYNITROAMINES Josef J. Schmidt-Collerus, Denver, Colo., Don N. Gray, Towson, Md., and Claibourne D. Smith, Eugene, 0reg., assignors to the United States of America as represented by the Secretary of the Air Force No Drawing. Filed Jan. 28, 1964, Ser. No. 340,836 Int. Cl. C07c 87/60 US. Cl. 260-576 3 Claims The invention relates to fluoro-substituted polynitroamines. More specifically, this invention relates to fluoroalkyl-substituted polynitrodiphenylamines having the general formula:

R X Y R1 l wherein R and R each represents a fluoro-alkyl radical having from 1 to 5 carbon atoms, X represents a nitro radical, and Y is selected from the group consisting of hydrogen and a nitro radical. Illustrative of the fluoroalkyl radicals represented by R and R are the following: -CF CH CF CH CHF CH CH F, CF CF CF(CF3)2. CH CH CF CH CH CH CF or other fluorine-containing alkyl groups in which the alkyl group may be either straight chained or branched in structure.

Various diphenylamines are well known for their utility in explosive applications. For example, hexanitrodiphenylamine, more commonly referredto as hexil, hexyl or hexite, is well known as both a primary explosive and a booster. This compound exhibits a greater explosive potential than either TNT or picric acid; but unfortunately is distinctly more sensitive to shock and heat. As a result, the utility of this compound has been appreciably lessened, especially when emploeyd under the severe conditions encountered during military field operations.

With the present invention, however, it has been discovered that the above noted prior art defects can be abrogated by providing a new class of fluoro-alkyl-substituted polynitrodiphenylamines. These compounds, although exhibiting a high explosive potential, are considerably more resistant to heat and shock and, therefore, do not suffer from the undesirable sensitivity of prior known diphenylamine explosives. As a result, the compounds of this invention have been found to be especially useful as primary explosives, detonators, boosters, and, in other explosive applications, utilized by the military. Additionally, the compounds of this invention are useful in the production of dyestuffs and the coloration of textile materials because of their unique afiinity for cellulosic materials.

Accordingly, the primary object of this invention is to provide a new class of explosive compounds which exhibit a high explosive potential together with a high degree of thermal and shock resistivity.

Another object of this invention is to provide a new class of fluoro-alkyl-substituted polynitrodiphenylamine compounds.

A further object of this invention is the preparation of novel dyestuffs and dyed textile materials.

3,562,332 Patented Feb. 9, 1971 "ice It has been found that the above stated objects can be accomplished by reacting chloro-substituted polynitrobenzotrifiuorides with an appropriate substituted amine. The resultant product from the aforementioned reaction can be nitrated to produce additional compounds which come within the scope of this invention as an additional embodiment thereof.

The novel features which are believed to be characteristic of this invention are set forth in the appended claims. However, the invention both as to its organization and method of operation may best be understood by referring to the following detailed examples which are presented as illustrative embodiments of the invention. These examples, however, are not to be construed as limiting the invention in any way.

EXAMPLE 1 Exactly 30.0 gms. of 3-chloro-2,4,6-trinitrobenzotrifluoride was dissolved in a solution consisting of 5.6 gins. of m-aminobenzotrifluoride in 20 ml. of absolute ethanol. The red platelets that precipitated were filtered, washed with sodium bicarbonate (1%), then n-hexane and subsequently air-dried. The resultant reaction product, 2,4,6- trinitro-3,3-di(trifluoromethyl) diphenylamine, had a melting point of 161162 C.

EXAMPLE 2 The reaction product from the process of Example 1, above, was nitrated at ambient temperature by dissolving the product in 20 ml. of sulfuric acid and adding drop-wise with stirring 10 ml. of fuming nitric acid. The reaction mixture was then poured onto crushed ice to yield a reaction product of 2,2',4,4-6,6'-heXanit1'o-3,3'-di-(trifluoromethyl)diphenylamine as an orange precipitate having a melting point of 234-236 C. A five percent solution of the compound produced by the process of this example dyes cotton cloth a yellow-gold. When the compound is dissolved in an ammonium solution, an intense coloration occurs followed by precipitation of the ammonium salt which has no definite melting point, but rather decomposes. The ammonium salt is soluble in both water and alcohol giving a red solution.

The new class of compounds disclosed by this invention have been found to be especially useful when employed in military applications as primary explosives since they exhibit a high explosive potential coupled with a minimum susceptibility to shock and heat. Additionally, these compounds are useful as dyestuffs as illustrated by referring to Example 2. In Example 2, a representative compound; namely, 2,2, 4,4,6,6-hexanitro-3,3'-di(trifluoromethyl)- diphenylamine, dyes cotton cloth a yellow-gold. It will be seen, therefore, that the instant invention provides a new class of compounds that are useful in explosive applications, the coloration of textile materials, and as intermediates in the production of new compounds.

It will be understood by those skilled in the art to which the present invention pertains, that while the compounds disclosed herein illustrate preferred embodiments of the invention, various modifications and alterations may be made without departing from the spirit and scope thereof, and that all such modifications as fall within the scope of the appended claims are intended to be included herein.

3 What is claimed is: 2. 2,4,6-trinitro-3,3'-di(trifiuoromethyl)diphenylamine. 1. The compounds having the formula: 3. 2,2,4,4,6,6' hexanitro-3,3-di(trifluorornethyl) diphenylamine. 1 H i References Cited X- 1lr -Y 5 -UNITED STATES PATENTS 3,418,372 12/1968 Taylor 149-105X X Y Where R and R each represents a fiuoro-alkyl radical hav- LELAND SEBASTIAN Pnmary Exammer ing from 1 to 5 carbon atoms, X represents a nitro radical 10 U S Cl X R and Y is selected from the group consisting of hydrogen and :1 nitro radical. 149105; 260-646 

1. THE COMPOUNDS HAVING THE FORMULA: 